Polyurethane resin for moisture-permeable water-proof materials, and polyurethane resin composition

ABSTRACT

The present invention aims to provide a polyurethane resin for moisture-permeable waterproof materials which is excellent in all of the moisture permeability, waterproofness, and resistance to washing. The polyurethane resin for moisture-permeable waterproof materials according to the present invention is a polyurethane resin for moisture-permeable waterproof materials, obtainable by reacting an active hydrogen component (A1) with an organic polyisocyanate component (B),
         wherein the active hydrogen component (A1) includes   an oxyethylene group-containing high molecular weight diol (a1), and   a compound (S1) containing at least one active hydrogen atom and being represented by the following formula (1):       

                         
wherein X 1  represents a residue produced by removing c piece(s) of active hydrogen atom(s) from an active hydrogen-containing compound having a valence of m, the c representing an integer satisfying the inequality: 1≦c≦m, the m representing an integer of 1 to 20;
         X 2  represents a residue produced by removing one piece of active hydrogen atom from an active hydrogen-containing compound, and a plurality of X 2 s may be the same as or different from one another;   X 1  and X 2  may be the same as or different from each other;   Y represents a residue produced by removing all of carboxyl groups from an aromatic polycarboxylic acid having a valence of 3 or more, wherein an aromatic ring in Y consists of carbon atoms, the carbon atoms are each optionally bound to a halogen atom and/or a substituent other than a carboxyl group, and at least one of the carbon atoms has no substituent;   a represents an integer of not smaller than 1;
           b represents an integer of not smaller than 0; and
 
a and b satisfy the inequality: 2≦a+b≦d−2, wherein d represents the number of hydrogen atoms bound to the carbon atoms forming the aromatic ring of the aromatic polycarboxylic acid when all of substituents including a carboxyl group in the aromatic polycarboxylic acid are substituted by hydrogen atoms, i.e., the number of substitutable sites on the aromatic ring.

TECHNICAL FIELD

The present invention relates to a polyurethane resin. Specifically, thepresent invention relates to a polyurethane resin that is suitably usedfor moisture-permeable waterproof materials.

BACKGROUND ART

Microporous sheets have been conventionally used as moisture-permeablematerials for moisture-permeable waterproof fabrics. Known examples ofsuch microporous sheets are those formed by stretching apolytetrafluoroethylene resin to form a porous sheet or polyurethaneresin films produced by wet film formation technique (see, for example,Patent Literature 1). Unfortunately, conventional porous sheets reducethe moisture permeability due to clogging with sweat, dirt, or othersubstances, or fail to exhibit sufficient waterproofness.

In order to overcome those disadvantages, non-porous sheets coated withhydrophilic moisture-permeable polyurethane resins have been proposed(see, for example, Patent Literatures 2 to 4). These moisture-permeablepolyurethane resins contain polyol components such as polyoxyethyleneglycol, which is a hydrophilic segment, and block copolymers ofpolyoxyethylene and polyoxypropylene.

Those non-porous sheets have a dramatically higher moisture permeabilitywhen they are coated with a thinner polyurethane resin film. However,those sheets have low strength due to low strength of resin and fail toexhibit sufficient waterproofness. Moreover, since the resin has a highpermanent set, those sheets have insufficient resistance to washingexemplified by plastic deformation of resin resulting in wrinkles afterwashing.

CITATION LIST Patent Literature

-   Patent Literature 1: JP-A S59-15825-   Patent Literature 2: JP-B S54-961-   Patent Literature 3: JP-A S64-62320-   Patent Literature 4: JP-A H04-180813

SUMMARY OF INVENTION Technical Problem

The present invention has been made in consideration of the abovedisadvantages, and aims to provide a polyurethane resin formoisture-permeable waterproof materials excellent in all of themoisture-permeability, waterproofness, and resistance to washing.

Solution to Problem

As a result of intensive studies to overcome the above disadvantages,the inventors of the present invention completed the present invention.The present invention provides a polyurethane resin (U) formoisture-permeable waterproof materials, obtainable by reacting anactive hydrogen component (A1) with an organic polyisocyanate component(B), wherein the active hydrogen component (A1) includes an oxyethylenegroup-containing high molecular weight diol (a1), and a compound (S1)containing at least one active hydrogen atom and being represented bythe following formula (1); and also provides a polyurethane resincomposition (W) for moisture-permeable waterproof materials, including apolyurethane resin, and a compound (S), the polyurethane resin beingobtainable by reacting an active hydrogen component (A2) that comprisesan oxyethylene group-containing high molecular weight diol (a1) otherthan the compound (S) with an organic polyisocyanate component (B), thecompound (S) being represented by the following formula (1).

In the formula (I), X¹ represents a residue produced by removing c piece(s) of active hydrogen atom(s) from an active hydrogen-containingcompound having a valence of m, the c representing an integer satisfyingthe inequality: 1≦c≦m, the m representing an integer of 1 to 20;

X² represents a residue produced by removing one piece of activehydrogen atom from an active hydrogen-containing compound, and aplurality of X²s may be the same as or different from one another;

X¹ and X² may be the same as or different from each other;

Y represents a residue produced by removing all of carboxyl groups froman aromatic polycarboxylic acid having a valence of 3 or more, whereinan aromatic ring in Y consists of carbon atoms, the carbon atoms areeach optionally bound to a halogen atom and/or a substituent other thana carboxyl group, and at least one of the carbon atoms has nosubstituent;

a represents an integer of not smaller than 1;

b represents an integer of not smaller than 0; and

a and b satisfy the inequality: 2≦a+b≦d−2, wherein d represents thenumber of hydrogen atoms bound to the carbon atoms forming the aromaticring of the aromatic polycarboxylic acid when all of substituentsincluding a carboxyl group in the aromatic polycarboxylic acid aresubstituted by hydrogen atoms, i.e., the number of substitutable siteson the aromatic ring.

Advantageous Effects of Invention

The polyurethane resin of the present invention has not only highhydrophilicity and high resin strength but also low permanent set. Thus,the use of the polyurethane resin of the present invention enables toprovide moisture-permeable waterproof materials that are excellent inmoisture permeability, waterproofness, and resistance to washing.

DESCRIPTION OF EMBODIMENTS

The polyurethane resin (U) for moisture-permeable waterproof materialsaccording to the present invention is characteristically obtainable byreacting an active hydrogen component (A1) with an organicpolyisocyanate component (B), the active hydrogen component (A1)including a compound (S1) containing at least one active hydrogen atomand being represented by the formula (1), and an oxyethylenegroup-containing high molecular weight diol (a1). The polyurethane resin(U) contains the active hydrogen component (A1) that at least partiallyincludes the compound (S1), so that the compound (S1) is incorporated inthe skeleton of the polyurethane resin (U). Thus, the polyurethane resinhas the specific effects mentioned above.

The polyurethane resin composition (W) for moisture-permeable waterproofmaterials according to the present invention includes a polyurethaneresin and a compound (S) represented by the formula (1). If apolyurethane resin that does not contain the compound (S1) containing atleast one active hydrogen atom and being represented by the formula (1)is mixed with the compound (S) represented by the formula (1), themixture exerts the same effects as those of the polyurethane resin (U)containing the compound (S1).

Examples of the compound (S) represented by the formula (1) include thecompound (S1) containing at least one active hydrogen atom and acompound (S2) containing no active hydrogen atom. The polyurethane resin(U) for moisture-permeable waterproof materials according to the presentinvention includes the compound (S1) containing at least one activehydrogen atom, among the compounds (S1) and (S2). The polyurethane resincomposition (W) for moisture-permeable waterproof materials according tothe present invention may include either of the compound (S1) and thecompound (S2).

One kind of the compound (S1) may be used alone, or two or more kindsthereof may be used in combination. The same applies to the compound(S2).

The following describes the compound (S) represented by the formula (1).The compositions, numeric values, and other items and ranges thereofmentioned as preferable for the compound (S) are the same in both of thecompound (S1) containing at least one active hydrogen atom to becontained in the polyurethane resin (U) and the compound (S) to becontained in the polyurethane resin composition (W), unless otherwisestated.

In the formula (1), X¹ represents a residue produced by removing cpiece(s) of active hydrogen atom(s) from an active hydrogen-containingcompound having a valence of m.

Examples of the active hydrogen-containing compound include hydroxygroup-containing compounds, ammonia, amino group-containing compounds,and thiol group-containing compounds. One kind of the activehydrogen-containing compound may be used alone, or two or more kindsthereof may be used in combination.

Examples of the hydroxy group-containing compounds include C₁-C₂₀monohydric alcohols, C₂-C₂₀ polyhydric alcohols, phenols, and alkyleneoxides (hereinafter abbreviated as AO) adducts thereof.

Examples of the C₁-C₂₀ monohydric alcohols include C₁-C₂₀ alkanol (e.g.,methanol, ethanol, butanol, octanol, decanol, dodecyl alcohol, myristylalcohol, cetyl alcohol, and stearyl alcohol), C₂-C₂₀ alkenol (e.g.,oleyl alcohol and linoleyl alcohol), and C₇-C₂₀ araliphatic alcohol(e.g., benzyl alcohol and naphthyl ethanol).

Examples of the C₂-C₂₀ polyhydric alcohols include C₂-C₂₀ dihydricalcohols, such as aliphatic diol (e.g., ethylene glycol, propyleneglycol, 1,3- or 1,4-butanediol, 1,6-hexanediol, neopentyl glycol, and1,10-decanediol), alicyclic diol (e.g., cyclohexanediol andcyclohexanedimethanol), and araliphatic diol (e.g., 1,4-bis(hydroxyethyl)benzene); C₃-C₂₀ trihydric alcohols, such as aliphatic triol(e.g., glycerin and trimethylol propane); and C₅-C₂₀ tetrahydric tooctahydric alcohols, such as aliphatic polyol (e.g., pentaerythritol,sorbitol, mannitol, sorbitan, diglycerin, and dipentaerythritol), andsaccharides (e.g., sucrose, glucose, mannose, fructose, methylglucoside, and derivatives thereof).

Examples of the phenols include monohydric phenol (e.g., phenol,1-hydroxy naphthalene, anthrol, and 1-hydroxy pyrene) and polyhydricphenol (e.g., phloroglucin, pyrogallol, catechol, hydroquinone,bisphenol A, bisphenol F, bisphenol S, 1,3,6,8-tetrahydroxy naphthalene,1,4,5,8-tetrahydroxy anthracene, condensates (Novolac) of phenol andformaldehyde, and polyphenols described in U.S. Pat. No. 3,265,641.

Examples of the amino group-containing compound include C₁-C₂₀monohydrocarbylamine, such as alkylamine (e.g., butyl amine), benzylamine, and aniline; C₂-C₂₀ aliphatic polyamine, such as ethylenediamine,1,6-hexane diamine, and diethylene triamine); C₆-C₂₀ alicyclicpolyamine, such as diamino cyclohexane, dicyclohexyl methanediamine, andisophoronediamine; C₂-C₂₀ aromatic polyamine, such as phenylene diamine,tolylenediamine, and diphenyl methanediamine; C₂-C₂₀ heterocyclicpolyamine, such as piperazine and N-amino ethyl piperazine;alkanolamines, such as monoethanolamine, diethanolamine, andtriethanolamine; polyamidepolyamines obtained by condensation ofdicarboxylic acid with an excess polyamine; polyether polyamines;hydrazines (e.g., hydrazine and monoalkyl hydrazines); dihydrazides(e.g., succinic acid dihydrazide and terephthalic acid dihydrazide);guanidines (e.g., butyl guanidine and 1-cyanoguanidine); anddicyandiamide.

Examples of the thiol group-containing compounds include C₁-C₂₀monovalent thiol compounds, such as alkane thiol (e.g., ethane thiol),benzene thiol, and phenyl methanethiol; and polythiol compounds, such as1,2-ethanedithiol and 1,6-hexanedithiol.

A compound having two or more kinds of active hydrogen-containingfunctional groups (e.g., hydroxy group, amino group, and thiol group) ina molecule thereof may be used as the active hydrogen-containingcompound.

Moreover, alkylene oxide (hereinafter abbreviated as AO) adducts of theabove-mentioned active hydrogen-containing compound may be used as theactive hydrogen-containing compound.

Examples of the AO to be added to the active-hydrogen containingcompound include C₂-C₄ AOs, such as ethylene oxide (hereinafterabbreviated as EO), 1,2-propylene oxide (hereinafter abbreviated as PO),1,3-propylene oxide, 1,2-, 1,3-, or 2,3-butylene oxide, andtetrahydrofuran (hereinafter abbreviated as THF). Preferable among theseare EO, PO and THF from the viewpoint of waterproofness and resistanceto washing. One kind of AO may be used alone, or two or more kinds ofAOs may be used in combination. A method of adding two or more kinds ofAOs may be block addition or random addition, or may be a combination ofthese methods.

The number of moles of the AO to be added is preferably 8 to 100, andmore preferably 10 to 80 from the viewpoint of waterproofness. Thehydroxyl value of the AO adduct is preferably 18 to 360 mg KOH/g.

In the present invention, the hydroxyl value is measured in accordancewith JIS K-1557-1.

Preferable examples of the active hydrogen-containing compound forintroducing X¹ into the compound (S) is preferably hydroxygroup-containing compounds, amino group-containing compounds, and AOadducts thereof from the viewpoint of waterproofness and resistance towashing. More preferable examples include C₂-C₂₀ polyhydric alcohols,polyether polyols obtained by adding AO to C₂-C₂₀ polyhydric alcohols,C₂-C₂₀ aliphatic polyamines, and polyvalent thiol compounds.Particularly preferable examples include C₂-C₂₀ polyhydric alcohols andpolyether polyols obtained by adding AO to C₂-C₂₀ polyhydric alcohols.Most preferable examples include polyether polyols obtained by adding AOto C₂-C₂₀ polyhydric alcohols.

The valence m of the active hydrogen-containing compound is normally 1to 20, preferably 1 to 8, more preferably 1 to 4, and particularlypreferably 2.

In the formula (1), c represents an integer satisfying the inequality:1≦c≦m. From the viewpoint of waterproofness and resistance to washing, cis preferably 1 to 8, more preferably 1 to 4, and particularlypreferably 2.

In the formula (1), X² represents a residue produced by removing onepiece of active hydrogen atom from an active hydrogen-containingcompound having 1 to 20 valences, and a plurality of X²s may be the sameas or different from one another.

The active hydrogen-containing compound for forming X² may be one thatis the same or similar to the active hydrogen-containing compoundmentioned for the above-mentioned X¹. X² and X¹ may be the same as ordifferent from each other; however, at least one of X²s is preferablydifferent from X¹ from the viewpoint of waterproofness and resistance towashing.

Moreover, the valence of X² is normally 1 to 20, preferably 1 to 8, 1more preferably 1 to 4, particularly preferably 1 to 2, and mostpreferably 2 from the viewpoint of waterproofness and resistance towashing.

Meanwhile, it is possible to introduce X¹ and X² in the compound (S) byreacting the active hydrogen-containing compound with a polycarboxylicacid having a valence of 3 or more to form the below-mentioned Y. In aspecific case where X¹ and X² each are a C₂ to C₄ diol, or a polyetherpolyol in which the repetition unit has 2 to 4 carbon atoms, the same orsimilar compound may also be obtained by adding the C₂-C₄ AO to thecarboxyl group of the polycarboxylic acid.

In the formula (1), Y represents a residue produced by removing all ofcarboxyl groups from an aromatic polycarboxylic acid having a valence of3 or more. An aromatic ring in Y consists of carbon atoms. The carbonatoms are each optionally bound to a halogen atom and/or a substituentother than a carboxyl group. Here, at least one of the carbon atoms hasno substituent and is bound to a hydrogen atom.

Examples of the substituent other than a carboxyl group include alkyl,vinyl, allyl, cyclo alkyl, amino, hydroxyl, hydroxy amino, nitro, thiol,aryl, and cyano groups.

Examples of the aromatic polycarboxylic acid having a valence of 3 ormore for forming Y include C₉ to C₃₀ aromatic polycarboxylic acids, forexample, tricarboxylic acids such as trimellitic acid, 1,2,3-benzenetricarboxylic acid, trimesic acid, hemimellitic acid, 1,2,4-, 1,3,6-, or2,3,6-naphthalene tricarboxylic acid, and 2,3,6-anthracene tricarboxylicacid; and tetracarboxylic acids such as pyromellitic acid,3,3′,4,4′-benzophenone tetracarboxylic acid, 2,2′,3,3′-benzophenonetetracarboxylic acid, 2,3,3′,4′-benzophenone tetracarboxylic acid,3,3′,4,4′-biphenyl tetracarboxylic acid, 2,2′,3,3′-biphenyltetracarboxylic acid, 2,3,3′,4′-biphenyl tetracarboxylic acid,4,4′-oxybis phthalic acid, diphenylmethane tetracarboxylic acid,1,4,5,8-naphthalene tetracarboxylic acid, 1,2,5,6-naphthalenetetracarboxylic acid, 2,3,6,7-naphthalene tetracarboxylic acid, and4,4′-(hexafluoroisopropylidene)bisphthalic acid. One kind of thearomatic polycarboxylic acid may be used alone, or two or more kindsthereof may be used in combination.

For production of the compound (S), ester-forming derivatives thereofmay be used, such as acid anhydride, lower alkyl (having 1 to 4 carbonatoms) ester (e.g., methyl ester, ethyl ester, and isopropyl ester), andacid halide (e.g., acid chlorides).

From the viewpoint of waterproofness and resistance to washing,preferable among the aromatic polycarboxylic acids are those having astructure in which carboxyl groups are respectively bound to two carbonatoms, which form the aromatic ring and are positioned adjacent to thecarbon atom having no substituent among the carbon atoms forming thearomatic ring. More preferably, a carboxyl group or groups is/arefurther bound to either one or both of carbon atoms that are adjacent tothe carbon atoms each bound to a carboxyl group.

For example, in the case where the aromatic ring of the aromaticpolycarboxylic acid is a benzene ring, the benzene ring preferably has astructure in which carboxyl groups are bound to carbon atoms of thefirst and third positions, and more preferably, in addition to thecarboxyl groups, a carboxyl group or groups is/are further bound to theeither one or both of carbon atoms of the fourth and sixth positions.

From the viewpoint of waterproofness and resistance to washing, thearomatic polycarboxylic acid for forming Y is particularly preferably amonocyclic compound, and most preferably trimellitic acid orpyromellitic acid.

In the formula (1), a represents an integer of not smaller than 1; brepresents an integer of not smaller than 0; and a and b satisfy theinequality: 2≦a+b≦d−2, wherein d represents the number of hydrogen atomsbound to the carbon atoms forming the aromatic ring of the aromaticpolycarboxylic acid when all of substituents including a carboxyl groupin the aromatic polycarboxylic acid are substituted by hydrogen atoms,i.e., the number of substitutable sites on the aromatic ring. Forexample, if the aromatic ring is a benzene ring consisting of six carbonatoms, d is 6, and a+b may be an integer from 2 to 4. If the aromaticring is a naphthalene ring consisting of 10 carbon atoms, d is 8, anda+b may be an integer from 2 to 6. If the aromatic ring is monocyclic,from the viewpoint of waterproofness and resistance to washing, a+b ispreferably 2 or 3. Moreover, from the viewpoint of waterproofness andresistance to washing, b is preferably an integer of not more than ahalf of a, and particularly preferably 0.

The compound (S) of the present invention preferably has a hydroxylvalue of 0, or 70 to 500 mg KOH/g from the viewpoint of waterproofnessand texture.

The compound (S1) has a hydroxyl value of preferably 70 to 500 mg KOH/g,and more preferably 75 to 350 mg KOH/g. If the compound (S1) has ahydroxyl value of less than 70 mg KOH/g, the polyurethane resin tends tohave low waterproofness. If it has a hydroxyl value of more than 500 mgKOH/g, the polyurethane resin tends to have inferior texture.

The compound (S2) has a hydroxyl value of 0.

The concentration of Yin the compound (S) means the amount (in mmol) ofthe residue Y in one gram of the compound (S), and it is preferably 1.0to 6.0 mmol/g, and more preferably 1.1 to 3.5 mmol/g from the viewpointof the waterproofness and resistance to washing of the polyurethaneresin. If the compound (S) includes the residue Y at a concentration ofless than 1.0 mmol/g, the polyurethane resin tends to have lowwaterproofness. If it includes the residue Y at a concentration of morethan 6.0 mmol/g, the polyurethane resin may have inferior texture.

The carbonyl group concentration in the compound (S) means the amount(in mmol) of the carbonyl group in one gram of the compound (S), and itis preferably 3.0 to 20 mmol/g, and more preferably 3.3 to 11 mmol/gfrom the viewpoint of the waterproofness and resistance to washing ofthe polyurethane resin. If the compound (S) has a carbonyl groupconcentration of less than 3.0 mmol/g, the polyurethane resin tends tohave low waterproofness. If it has a carbonyl group concentration ofmore than 20 mmol/g, the texture may be deteriorated.

The compound (S) has a molar average number of functional groups ofpreferably 0 to 8, more preferably 2 to 6, and particularly preferably 2to 4 from the viewpoint of the waterproofness of the polyurethane resin.

The molar average number of functional groups according to the presentinvention is a value obtained by multiplying the number of activehydrogen-containing functional groups of a component by the number ofmoles of the component to give a product, summing up the products forall the components in a composition, and then dividing the total valueby a sum of the numbers of moles of all the components. The number ofmoles of each component is a value obtained by dividing the weight ofeach component by the molecular weight of the component. The molecularweight for the calculation is the chemical formula weight if thecomponent has no molecular weight distribution as in the case of lowmolecular weight compounds. The molecular weight for the calculation isthe number average molecular weight (hereinafter abbreviated as Mn) ifthe component has a molecular weight distribution. The Mn values of thecompound (S) and polyol in the present invention are measured by gelpermeation chromatography (GPC) using THF as a solvent andpolyoxypropylene glycol as a standard. For the measurement, theconcentration of samples is 0.25% by weight, the column stationary phaseis a combination of a TSKgel Super H2000, a TSKgel Super H3000, and aTSKgel Super H4000 (all produced by TOSOH Corporation), and the columntemperature is 40° C.

The compound (S1) containing at least one active hydrogen atom to beincorporated into the polyurethane resin (U) skeleton is a compoundrepresented by the formula (1) in which at least one of X¹, X² and Y hasan active hydrogen atom. Specifically, the compound (S1) contains atleast one active hydrogen atom in at least one of the followingconditions: the valences m and c of X¹ satisfy m>c; Y is replaced by asubstituent having an active hydrogen atom, such as an amino group, ahydroxyl group, a hydroxyamino group, and a thiol group; the activehydrogen-containing compound forming X² is a di- or higher valentcompound; or b is an integer of not less than 1.

The amount of the compound (S1) to be incorporated into the skeleton ofthe polyurethane resin (U) is preferably 0.01 to 10% by weight, and morepreferably 0.02 to 5% by weight based on a total weight of the activehydrogen component (A1) and organic polyisocyanate component (B) fromthe viewpoint of waterproofness and resistance to washing.

Examples of the oxyethylene group-containing high molecular weight diol(a1) in the present invention include EO adducts of the C₂-C₂₀polyhydric alcohols (e.g., polyoxyethylene glycol), polyadducts of EOand other AO, and EO adducts of other high molecular weight diol (a2)mentioned below.

Examples of other AO include PO, 1,2-, 1,3- or 2,3-buthyrene oxide, andTHF, and a combination of two or more of these.

A method of adding EO to other AO may be random addition or blockaddition, or may be a combination of these methods.

Preferable among these from the viewpoint of moisture permeability arepolyoxyethylene glycol, and polyadducts of EO and other AO to C₂-C₂₀dihydric alcohol; more preferably polyoxyethylene glycol, and randompolyadducts of EO and PO to propylene glycol or ethylene glycol; andmost preferably polyoxyethylene glycol. One kind of the oxyethylenegroup-containing high molecular weight diol (a1) may be used alone, ortwo or more kinds thereof may be used in combination.

The oxyethylene group-containing high molecular weight diol (a1) has ahydroxyl value of preferably 2 to 150 mg KOH/g, and more preferably 5 to70 mg KOH/g from the viewpoint of waterproofness and texture. If theoxyethylene group-containing high molecular weight diol (a1) has ahydroxyl value of less than 2 mg KOH/g, the polyurethane resin tends tohave low waterproofness. If it has a hydroxyl value of more than 150 mgKOH/g, the polyurethane resin may have inferior texture.

The amount of the oxyethylene group to be introduced into thepolyurethane resin (U) by the oxyethylene group-containing highmolecular weight diol (a1) is preferably 20 to 80% by weight, and morepreferably 30 to 60% by weight based on the weight of the polyurethaneresin (U) from the viewpoint of moisture permeability and resistance towashing. If the amount is less than 20% by weight, the moisturepermeability tends to decrease. If the amount is more than 80% byweight, the resistance to washing tends to decrease.

The active hydrogen component (A1) may further contain other highmolecular weight diol (a2) as long as the moisture permeability of thepolyurethane resin (U) is not deteriorated.

Examples of other high molecular weight diol (a2) include polyether dioland polyester diol.

Examples of the polyether diol include polyoxypropylene glycol,polyoxytetramethylene glycol, polyoxypropylene/polyoxytetramethyleneblock copolymer diol.

Examples of the polyester diol include condensed polyester diol,polylactone diol, and polycarbonate diol.

The condensed polyester diol is obtainable by reacting the C₂-C₂₀dihydric alcohol with a C₂-C₂₀ dicarboxylic acid.

Examples of the C₂-C₂₀ dicarboxylic acid include aliphatic dicarboxylicacids (e.g., succinic acid, adipic acid, and sebacic acid), aromaticdicarboxylic acids (e.g., terephthalic acid and isophthalic acid), andmixtures of two or more kinds thereof.

Specific examples of the condensed polyester diol include polyethyleneadipate diol, polybutylene adipate diol, poly hexamethylene adipatediol, polyhexamethylene isophthalate diol, polyneopentyl adipate diol,polyethylene propylene adipate diol, polyethylene buthylene adipatediol, polybutylene hexamethylene adipate diol, polydiethylene adipatediol, poly(polytetramethylene ether)adipate diol, poly(3-methylpentylene adipate)diol, polyethylene azelate diol, polyethylene sebacatediol, polybutylene azelate diol, polybutylene sebacate diol, andpolyneopentyl terephthalate diol.

The polylactone diol is a polyadduct of lactone to the C₂-C₂₀ dihydricalcohol. Examples of the lactone include C₄-C₁₂ lactones (e.g.,γ-butyrolactone, γ-valerolactone, and ε-caprolactone).

Specific examples of the polylactone polyol include polycaprolactonediol, polyvalerolactone diol, and polycaprolactone triol.

Examples of the polycarbonate diol include polycarbonate polyolsproduced by condensation through dealcoholization reaction of the C₂-C₂₀dihydric alcohol and a low molecular weight carbonate compound (e.g.,dialkyl carbonates containing C₁-C₆ alkyl groups, alkylene carbonatescontaining C₂-C₆ alkylene groups, and diaryl carbonates containing C₆-C₉aryl groups). Each of the C₂-C₂₀ dihydric alcohol and the low molecularweight carbonate compound may be used in a combination of two or morekinds thereof.

Specific examples of the polycarbonate polyols include polyhexamethylenecarbonate diols, polypentamethylene carbonate diols, polytetramethylenecarbonate diols, and poly(tetramethylene/hexamethylene)carbonate diols(e.g., diols produced by condensation through dealcoholization reactionof 1,4-butanediol and 1,6-hexanediol with dialkyl carbonate).

The other high molecular weight diol (a2) has a hydroxyl value ofpreferably 2 to 150 mg KOH/g, and more preferably 5 to 70 mg KOH/g fromthe viewpoint of waterproofness and texture. If the high molecularweight diol (a2) has a hydroxyl value of less than 2 mg KOH/g, thepolyurethane resin tends to have low waterproofness. If it has ahydroxyl value of more than 150 mg KOH/g, the polyurethane resin tendsto have inferior texture.

The active hydrogen component (A1) may further contain a chain extender(a3) and a reaction terminator (a4).

Examples of the chain extender (a3) include water, the C₂-C₂₀ polyhydricalcohol, C₂-C₁₀ diamines (e.g., ethylenediamine, propylene diamine,1,6-hexane diamine, isophorone diamine, toluene diamine and piperazine),polyalkylene polyamines (e.g., diethylene triamine, and triethylenetetramine), hydrazines and derivatives thereof (e.g., dibasic aciddihydrazide such as adipic acid dihydrazide), and C₂-C₁₀ amino alcohols(e.g., ethanol amine, diethanolamine, 2-amino-2-methyl propanol, andtriethanolamine). One kind of the chain extender may be used alone, ortwo or more kinds thereof may be used in combination.

Examples of the reaction terminator (a4) include C₁-C₈ monoalcohols(e.g., methanol, ethanol, isopropanol, n-butanol, cellosolves, andcarbitols) and C₁-C₁₀ monoamines (e.g., mono- or di-alkylamines, such asmonomethylamine, monoethylamine, monobutylamine, dibutylamine, andmonooctylamine; mono- or di-alkanolamines, such as monoethanolamine,diethanolamine, and diisopropanolamine). One kind of the reactionterminator may be used alone, or two or more kinds thereof may be usedin combination.

Any organic polyisocyanate which is usually used for production ofpolyurethane resins may be used as the organic polyisocyanate component(B) in the present invention. Examples thereof include an aromaticpolyisocyanate, an aliphatic polyisocyanate, an alicyclicpolyisocyanate, an araliphatic polyisocyanate, and modified compoundsthereof (urethane group-, carbodiimide group-, allophanate group-, ureagroup-, biuret group-, isocyanurate group- and oxazolidonegroup-containing modified polyisocyanates and the like). One kind of thepolyisocyanate component (B) may be used alone, or two or more kindsthereof may be used in combination.

Examples of the aromatic polyisocyanate include C₆-C₁₆ (excluding carbonatoms in an NCO group; the same shall apply to the followingpolyisocyanates) aromatic diisocyanates, C₆-C₂₀ aromatic triisocyanates,and crude compounds of these isocyanates. Specific examples thereofinclude 1,3- or 1,4-phenylene diisocyanate, 2,4- or 2,6-tolylenediisocyanate (hereinafter abbreviated as TDI), crude TDI, 2,4′- or4,4′-diphenylmethane diisocyanate (hereinafter abbreviated as MDI),polymethylene-polyphenylene polyisocyanate (hereinafter abbreviated ascrude MDI), naphthylene-1,5-diisocyanate, andtriphenylmethane-4,4′,4″-triisocyanate.

Examples of the aliphatic polyisocyanate include C₆ to C₁₀ aliphaticdiisocyanate, such as 1,6-hexamethylene diisocyanate, 2,2,4-trimethylhexamethylene diisocyanate, and lysine diisocyanate.

Examples of the alicyclic polyisocyanate include C₆ to C₁₆ alicyclicdiisocyanate, such as isophorone diisocyanate, 4,4′-dicyclohexylmethanediisocyanate, 1,4-cyclohexane diisocyanate, and norbornane diisocyanate.

Examples of the araliphatic isocyanate include C₈ to C₁₂ araliphaticdiisocyanate, such as xylylene diisocyanate andα,α,α′,α′-tetramethylxylylene diisocyanate.

Specific examples of the modified polyisocyanates includecarbodiimide-modified MDI.

Among these, an aromatic polyisocyanate is preferable; and TDI, crudeTDI, MDI, crude MDI and modified compounds of these isocyanates are morepreferable from the viewpoint of tensile strength. Particularlypreferably, MDI, crude MDI, and modified compounds of these isocyanatesare contained in a total amount of not less than 10% by weight (inparticular 15 to 80% by weight). The isocyanate group content (NCO %) inthe entire organic polyisocyanate component (B) is preferably 25 to 45%by weight.

The polyurethane resin (U) for moisture-permeable waterproof materialsaccording to the present invention has a weight average molecular weight(Mw) of preferably 50,000 to 1,000,000, and more preferably 100,000 to500,000 from the viewpoint of enhancement in the tensile strength.

In the present invention, the Mw of the polyurethane resin is measuredby gel permeation chromatography (GPC) using dimethylformamide(hereinafter abbreviated as DMF) as a solvent and polystyrene as astandard. For the measurement, the concentration of samples is 0.25% byweight, the column stationary phase is a combination of a TSKgel SuperH2000, a TSKgel Super H3000, and a TSKgel Super H4000 (all produced byTOSOH Corporation), and the column temperature is 40° C.

The polyurethane resin for moisture-permeable waterproof materialsaccording to the present invention is produced by any method, and may beproduced by known methods or other methods. For example, the activehydrogen component (A1), the polyisocyanate component (B), andoptionally an organic solvent and an additive may be introduced alltogether for a reaction. Alternatively, the active hydrogen component(A1) is reacted with the polyisocyanate component (B) to obtain aprepolymer having terminal isocyanate groups, and then a chain extensionreaction is caused by the chain extender. Moreover, the reaction may beperformed by use of a kneader or the like as a reaction device withoutany solvent.

Any polyurethane resin may be used for the polyurethane resincomposition (W) as long as it contains the oxyethylene group-containinghigh molecular weight diol (a1) as a structural unit of the resinmolecule. The polyurethane resin may or may not contain the compound(S1) as a component of the molecule. Examples of the polyurethane resininclude those obtainable by reacting the following: an active hydrogencomponent (A2) containing the oxyethylene group-containing highmolecular weight diol (a1) and optionally containing the above-mentionedother high molecular weight diol (a2), chain extender (a3), reactionterminator (a4), and compound (S1); and the organic polyisocyanatecomponent (B).

If the compound (S) is added to the polyurethane resin, the amount to beadded is preferably 0.01 to 10% by weight, and more preferably 0.02 to5% by weight based on the weight of the polyurethane resin.

During the production of the polyurethane resin composition (W), thepolyurethane resin and the compound (S) may be added at any time. Thecompound (S) may be added after producing the polyurethane resin. In thecase where the compound (S) is the compound (S2) containing no activehydrogen atom, the polyurethane resin may be produced in the presence ofthe compound (S2).

The preferable range of the oxyethylene group content in thepolyurethane resin to be contained in the polyurethane resin composition(W) is the same as or similar to the preferable range in the case of thepolyurethane resin (U).

The polyurethane resin (U) for moisture-permeable waterproof materialsaccording to the present invention, which is optionally mixed with anorganic solvent, may be used as an organic solvent solution. Thepolyurethane resin composition (W) of the present invention mayoptionally contain an organic solvent.

Examples of the organic solvent include solvents containing no activehydrogen group, and specific examples thereof include amide-typesolvents (e.g. DMF, N,N-dimethylacetamide, N-methylpyrrolidone),sulfoxide-type solvents (e.g., dimethyl sulfoxide), ketone-type solvents(e.g., methyl ethyl ketone, methyl isobutyl ketone), ether-type solvents(e.g., dioxane, THF), ester-type solvents (e.g., methyl acetate, ethylacetate, butyl acetate), and aromatic-type solvents (e.g., toluene,xylene). One kind of the organic solvent may be used alone, or two ormore kinds thereof may be used in combination.

The polyurethane resin (U) of the present invention may be used afteroptionally mixed with a pigment, a stabilizer, or other additives. Thepolyurethane resin composition (W) of the present invention mayoptionally contain a pigment, a stabilizer, or other additives.

Any known organic pigments and/or inorganic pigments may be used as apigment. The amount of the pigment to be added is usually 0 to 5% byweight, and preferably 0.1 to 3% by weight relative to the polyurethaneresin. Examples of the organic pigments include insoluble azo pigments,soluble azo pigments, copper phthalocyanine pigments, and quinacridonepigments. Examples of the inorganic pigments include chromate salts,ferrocyanide compounds, metal oxides, selenium sulfide compounds, metalsalts (e.g., sulfate, silicate, carbonate, phosphate), metal powders,and carbon black.

Any stabilizer may be used, and known antioxidants and/or ultravioletabsorbers may be used as a stabilizer. The amount of the stabilizer isusually 0 to 5% by weight, and preferably 0.1 to 3% by weight relativeto the polyurethane resin.

Examples of the antioxidants include phenol-type antioxidants (e.g.,2,6-di-t-butyl-p-crezol, butylated hydroxy anisole); bisphenol-typeantioxidants (e.g., 2,2′-methylene bis(4-methyl-6-t-butyl phenol)); andphosphorus-type antioxidants (e.g., triphenyl phosphite, diphenylisodecyl phosphite).

Examples of the ultraviolet absorbers include benzophenone-typeultraviolet absorbers (e.g. 2,4-dihydroxy benzophenone,2-hydroxy-4-methoxy benzophenone); benzotriazole-type ultravioletabsorbers (e.g. 2-(2′-hydroxy-5′-methyl phenyl)benzotriazole);salicylate-type ultraviolet absorbers (e.g. phenylsalicylate); andhindered amine-type ultraviolet absorbers (e.g.bis(2,2,6,6-tetramethyl-4-piperiridyl)sebacate). Examples of otheradditives include fusion inhibitors and flame retardants.

The pigment, stabilizer, and other additive may be added at any stageduring the production of the polyurethane resin, or after theproduction. Moreover, in the case where the polyurethane resincomposition (W) contains the pigment, stabilizer, or other additives,such an additive may be added at any stage during the production of thepolyurethane resin, or after the production.

The polyurethane resin (U) and polyurethane resin composition (W) of thepresent invention each are used as a polyurethane resin layer of amoisture-permeable waterproof material, which is a composite materialincluding a fiber material and a polyurethane resin layer provided on atleast one surface of the fiber material.

The base materials of the fiber material may be any of cellulose fiberssuch as cotton, linen, and rayon; and synthetic fibers such aspolyester, polyamide, and polyolefin. The fiber material may be in anyform of fabric, such as woven, knitted, and nonwoven fabrics, and ispreferably a woven or knitted fabric.

The moisture-permeable waterproof material including the polyurethaneresin (U) or polyurethane resin composition (W) of the present inventionis favorably used for wears for outdoor activities such as fishing andmountain climbing, skiing wears, wind breakers, athletic wears, golfwears, rain wears, casual coats, outdoor work wears, gloves, shoes, andmountaineering equipment such as tents, or the like.

EXAMPLES

The present invention will be described in more detail below based onexamples which, however, are not intended to limit the presentinvention. Hereinafter, the term “parts” means “parts by weight.”

Production Example 1 Production of Compound (S1-1)

A PO/EO block adduct of propylene glycol (900 parts, “SANNIX PL-910”produced by Sanyo Chemical Industries, Ltd., Mn: 900, hydroxyl value:124.7), 384 parts of trimellitic anhydride, and 1.0 part of an alkalicatalyst (N-ethylmorpholine) were charged into a stainless steelautoclave equipped with a stirrer and a temperature controller. Theywere reacted under a nitrogen atmosphere at 0.20 MPa and 130±10° C. for5 hours for half esterification of the acid anhydride functional groupto give an ester compound in which 2 moles of the trimellitic anhydridewas reacted with 1 mole of the PO/EO block adduct of propylene glycol.Subsequently, 198 parts of EO was added dropwise over 5 hours whilecontrolling the pressure to 0.50 MPa or less at 100±10° C., followed byaging at 100±10° C. for 1 hour. In this manner, a compound (S1-1) inwhich EO was added to the carboxyl groups of the ester compound wasobtained.

Production Example 2 Production of Compound (S1-2)

A compound (S1-2) was obtained in the same manner as in ProductionExample 1, except that 1000 parts of polyoxytetramethylene glycol(“PTMG1000” produced by Mitsubishi Chemical Corporation, Mn: 1000,hydroxyl value: 112.2) was used instead of the 900 parts of the PO/EOblock adduct of propylene glycol.

Production Example 3 Production of Compound (S1-3)

A compound (S1-3) was obtained in the same manner as in ProductionExample 1, except that 1500 parts of polyoxypropylene triol (“SANNIXGP-1500” produced by Sanyo Chemical Industries, Ltd., Mn: 1500, hydroxylvalue: 112.2) was used instead of the 900 parts of PO/EO block adduct ofpropylene glycol; and the amounts of trimellitic anhydride and EOcharged were changed to 576 parts and 299 parts, respectively.

Production Example 4 Production of Compound (S1-4)

A compound (S1-4) was obtained in the same manner as in ProductionExample 1, except that 1000 parts of polyoxypropylene glycol (“SANNIXPP-1000” produced by Sanyo Chemical Industries, Ltd., Mn: 1000, hydroxylvalue: 112.2) was used instead of the 900 parts of PO/EO block adduct ofpropylene glycol; and the amount of EO charged was changed to 101 parts.

Production Example 5 Production of Compound (S1-5)

A compound (S1-5) was obtained in the same manner as in ProductionExample 1, except that 1000 parts of polyoxyethylene glycol (“PEG-1000”produced by Sanyo Chemical Industries, Ltd., Mn: 1000, hydroxyl value:112.2) was used instead of the 900 parts of PO/EO block adduct ofpropylene glycol.

Production Example 6 Production of Compound (S1-6)

A compound (S1-6) was obtained in the same manner as in ProductionExample 1, except that 200 parts of polyoxyethylene glycol (“PEG-200”produced by Sanyo Chemical Industries, Ltd., Mn: 200, hydroxyl value:561.0) was used instead of the 900 parts of PO/EO block adduct ofpropylene glycol.

Production Example 7 Production of Compound (S1-7)

A compound (S1-7) was obtained in the same manner as in ProductionExample 1, except that 62 parts of ethylene glycol was used instead ofthe 900 parts of PO/EO block adduct of propylene glycol.

Production Example 8 Production of Compound (S1-8)

An amount of 116 parts of 1,6-hexane diamine, 384 parts of trimelliticanhydride, 1.0 part of an alkali catalyst (N-ethylmorpholine), and 246parts of THF as a solvent were charged into a stainless steel autoclaveequipped with a stirrer and a temperature controller. They were reactedunder a nitrogen atmosphere at 80±10° C. for 2 hours for half amidationof the acid anhydride functional group to give an amide compound inwhich 2 moles of the trimellitic anhydride was reacted with 1 mole ofthe 1,6-hexane diamine. Subsequently, 198 parts of EO was added dropwiseover 5 hours while controlling the pressure to 0.50 MPa or less at80±10° C., followed by aging at 80±10° C. for 1 hour. Thereafter, thesolvent was evaporated at 10 kPa at 80±10° C. In this manner, a compound(S1-8) in which EO was added to the carboxyl groups of the amidecompound was obtained.

Production Example 9 Production of Compound (S1-9)

An amount of 150 parts of 1,6-hexane dithiol, 384 parts of trimelliticanhydride, 0.1 part of a ruthenium chloride (III) catalyst, and 246parts of THF as a solvent were charged into a stainless steel autoclaveequipped with a stirrer and a temperature controller. They were reactedunder a nitrogen atmosphere at 50±10° C. for 2 hours for halfthioesterification of the acid anhydride functional group to give athioester compound in which 2 moles of the trimellitic anhydride wasreacted with 1 mole of the 1,6-hexane dithiol. Subsequently, 198 partsof EO was added dropwise over 5 hours while controlling the pressure to0.50 MPa or less at 80±10° C., followed by aging at 80±10° C. for 1hour. Thereafter, the solvent was evaporated at 10 kPa at 80±10° C. Inthis manner, a compound (S1-9) in which EO was added to the carboxylgroups of the thioester compound was obtained.

Production Example 10 Production of Compound (S1-10)

A compound (S1-10) was obtained in the same manner as in ProductionExample 1, except that 400 parts of polyoxyethylene glycol (“PEG-200”produced by Sanyo Chemical Industries, Ltd., Mn: 200, hydroxyl value:561.0) was used instead of the 900 parts of PO/EO block adduct ofpropylene glycol; 218 parts of pyromellitic anhydride was used insteadof the 384 parts of trimellitic anhydride; and the amount of the EOcharged was changed to 99 parts.

Production Example 11 Production of Compound (S1-11

A compound (S1-11) was obtained in the same manner as in ProductionExample 1, except that 484 parts of naphthalene-1,2,4-tricarboxylicacid-1,2-anhydride was used instead of the 384 parts of trimelliticanhydride.

Production Example 12 Production of Compound (S1-12)

An amount of 62 parts of ethylene glycol, 192 parts of trimelliticanhydride, and 1.0 part of an alkali catalyst (N-ethylmorpholine) werecharged into a stainless steel autoclave equipped with a stirrer and atemperature controller. They were reacted under a nitrogen atmosphere at0.20 MP and at 130±10° C. for 5 hours for half esterification of theacid anhydride functional group to give an ester compound in which 1mole of the trimellitic anhydride was reacted with 1 mole of theethylene glycol. Subsequently, 99 parts of EO was added dropwise over 5hours while controlling the pressure to 0.50 MPa or less at 100±10° C.,followed by aging at 100±10° C. for 1 hour. In this manner, a compound(S1-12) in which EO was added to the carboxyl groups of the estercompound was obtained.

Production Example 13 Production of Compound (S2-1)

A PO/EO block adduct of propylene glycol (900 parts, “SANNIX PL-910”produced by Sanyo Chemical Industries, Ltd., Mn: 900, hydroxyl value:124.7), 384 parts of trimellitic anhydride, and 404 parts oftriethylamine were charged into a stainless steel autoclave equippedwith a stirrer and a temperature controller. They were reacted under anitrogen atmosphere at 0.20 MPa and at 80±5° C. for 2 hours for halfesterification of the acid anhydride functional group to give an estercompound in which 2 moles of the trimellitic anhydride was reacted with1 mole of the PO/EO block adduct of propylene glycol. Next, 508 parts ofbenzyl chloride was further added, followed by reaction at 70±5° C. for2 hours and subsequently separation of the liquid. In this manner, acompound (S2-1) in which the carboxyl groups of the ester compound weresubstituted by a benzyloxycarbonyl group was obtained.

Comparative Production Example 1 Production of Compound (S1′-1)

A polyol (S1′-1) was obtained in the same manner as in ProductionExample 1, except that 3200 parts of polyoxypropylene triol (“SANNIXGP-3000” produced by Sanyo Chemical Industries, Ltd., Mn: 3200, hydroxylvalue: 52.6) was used instead of the 900 parts of PO/EO block adduct ofpropylene glycol; 444 parts of phthalic anhydride was used instead ofthe 384 parts of trimellitic anhydride; and the amount of EO charged waschanged to 149 parts.

Comparative Production Example 2 Production of Compound (S1′-2)

A polyol (S1′-2) was obtained in the same manner as in ProductionExample 1, except that 296 parts of phthalic anhydride was used insteadof the 384.0 parts of trimellitic anhydride; and the amount of the EOcharged was changed to 99.0 parts.

Table 1 shows the results of analysis of the compounds obtained inProduction Examples 1 to 13, and Comparative Production Examples 1 to 2.

TABLE 1 Carbonyl group Molar average In Compound Hydroxyl valueConcentration of concentration number of formula (1) (S) (mgKOH/g) γ(mmol/g) (mmol/g) functional groups Mn a b c Production Example 1 (S1-1)151.4 1.3 4.0 4 1482 2 0 2 Production Example 2 (S1-2) 141.8 1.3 3.8 41582 2 0 2 Production Example 3 (S1-3) 141.7 1.3 3.8 6 2375 2 0 3Production Example 4 (S1-4) 151.1 1.3 4.0 4 1485 1 1 2 ProductionExample 5 (S1-5) 141.8 1.3 3.8 4 1582 2 0 2 Production Example 6 (S1-6)287.0 2.6 7.7 4 782 2 0 2 Production Example 7 (S1-7) 348.4 3.1 9.3 4644 2 0 2 Production Example 8 (S1-8) 321.5 2.9 5.7 4 698 2 0 2Production Example 9 (S1-9) 306.6 2.7 5.5 4 732 2 0 2 Production Example10 (S1-10) 313.0 1.4 5.6 4 717 3 0 1 Production Example 11 (S1-11) 141.81.3 3.8 4 1582 2 0 2 Production Example 12 (S1-12) 476.8 2.8 8.5 3 353 20 1 Production Example 13 (S2-1) 0 3.6 3.6 0 1644 2 0 2 ComparativeProduction (S1′-1) 44.4 0.8 1.6 3 3793 1 0 3 Example 1 ComparativeProduction (S1′-2) 86.6 1.5 3.1 2 1295 1 0 2 Example 2

Examples 1 to 13 and Comparative Examples 1 to 3

According to the formulations shown in Table 2, a compound (S1) in anactive hydrogen component (A1), a polyol (a1), a chain extender (a3), anorganic polyisocyanate component (B), and a solvent were charged into areactor. They were reacted under a dry nitrogen atmosphere at 70° C. for12 hours, and then a reaction terminator (a4) was added thereto toperform end-terminating reaction for 1 hour. In this manner, solutionsof the polyurethane resins (U-1) to (U-13) of the present invention andcomparative solutions of polyurethane resins (U′-1) to (U′-3) wereobtained.

TABLE 2 Exam- Example 1 Example 2 Example 3 Example 4 Example 5 Example6 Example 7 ple 8 Code of polyurethane resin U-1 U-2 U-3 U-4 U-5 U-6 U-7U-8 Active Compound (S1) Compound (S1-1) 0.167 — — — — — — — hydrogenCompound (S1-2) — 0.167 — — — — — — component Compound (S1-3) — — 0.167— — — — — (A1) (parts) Compound (S1-4) — — — 16.7 — — — — Compound(S1-5) — — — — 0.167 — — — Compound (S1-6) — — — — — 0.05 — — Compound(S1-7) — — — — — — 0.167 — Compound (S1-8) — — — — — — — 0.167 Compound(S1-9) — — — — — — — — Compound (S1-10) — — — — — — — — Compound (S1-11)— — — — — — — — Compound (S1-12) — — — — — — — — Comparative polyol — —— — — — — — (S1′-1) Comparative polyol — — — — — — — — (S1′-2) Polyol(a1) Polyoxyethylene 200 200 200 200 200 200 200 200 glycol (Mn: 4000)Chain Ethylene glycol 23.1 23.1 23.1 23.1 23.1 23.1 23.1 23.1 extender(a3) Reaction n-Butanol 5.6 5.6 5.6 5.6 5.6 5.6 5.6 5.6 terminator (a4)Organic MDI 110 110 110 110 110 110 110 110 polyisocyanate component (B)(parts) Organic DMF 777 777 777 777 777 777 777 777 solvent (parts)Exam- Exam- Exam- Exam- Exam- Comparative Comparative Comparative ple 9ple 10 ple 11 ple 12 ple 13 Example 1 Example 2 Example 3 Code ofpolyurethane resin U-9 U-10 U-11 U-12 U-13 U′-1 U′-2 U′-3 ActiveCompound (S1) Compound (S1-1) — — — — 16.9 — — — hydrogen Compound(S1-2) — — — — — — — — component Compound (S1-3) — — — — — — — — (A1)(parts) Compound (S1-4) — — — — — — — — Compound (S1-5) — — — — — — — —Compound (S1-6) — — — — — — — — Compound (S1-7) — — — — — — — — Compound(S1-8) — — — — — — — — Compound (S1-9) 0.167 — — — — — — — Compound(S1-10) — 1.67 — — — — — — Compound (S1-11) — — 0.167 — — — — — Compound(S1-12) — — — 0.167 — — — — Comparative polyol — — — — — — 0.167 —(S1′-1) Comparative polyol — — — — — — — 0.167 (S1′-2) Polyol (a1)Polyoxyethylene 200 200 200 200 200 200 200 200 glycol (Mn: 4000) ChainEthylene glycol 23.1 23.1 23.1 23.1 23.1 23.1 23.1 23.1 extender (a3)Reaction n-Butanol 5.6 5.6 5.6 5.6 5.6 5.6 5.6 5.6 terminator (a4)Organic MDI 110 110 110 110 110 110 110 110 polyisocyanate component (B)(parts) Organic DMF 777 777 777 777 777 777 777 777 solvent (parts)

Examples 14 to 16 and Comparative Example 4

According to the formulations shown in Table 3, a polyol (a1) in anactive hydrogen component (A2), a chain extender (a3), an organicpolyisocyanate component (B), and a solvent were charged into a reactor.They were reacted under a dry nitrogen atmosphere at 70° C. for 12hours, and then a reaction terminator (a4) was added thereto to performend-terminating reaction for 1 hour. Thereafter, a compound (S) as anadditive shown in Table 3 was added, followed by stirring at 60° C. for15 minutes. In this manner, the polyurethane resin compositions (W-1) to(W-3) and a comparative polyurethane resin composition (W′-1) wereobtained.

TABLE 3 Comparative Example 14 Example 15 Example 16 Example 4 Code ofpolyurethane resin composition W-1 W-2 W-3 W′-1 Active hydrogen Polyol(a1) Polyoxyethylene glycol (Mn: 200 200 200 200 component (A2) (parts)4000) Chain extender (a3) Ethylene glycol 23.1 23.1 23.1 23.1 Reactionterminator n-Butanol 5.6 5.6 5.6 5.6 (a4) Organic polyisocyanatecomponent (B) (parts) MDI 110 110 110 110 Organic solvent (parts) DMF777 777 777 777 Compound (S) as an additive (parts) Compound (S1-1)0.167 — 14.2 — Compound (S2-1) — 0.167 — — Comparative compound — — —0.167 (S1′-1)

Table 4 shows the results of measurements or evaluations on the tensilestrength, permanent set, moisture permeability, resistance to waterpressure, and resistance to washing, and the compound (S) content andthe amount of the compound (S) added, of the polyurethane resinsolutions and the polyurethane resin compositions obtained in Examples 1to 16 and Comparative Examples 1 to 4.

Meanwhile, the item “Compound (S1) content (%) in polyurethane resin” inTable 4 refers to the compound (S1) content (% by weight, excluding thecompound (S1′)) in the active hydrogen component (A1) based on the totalweight of the active hydrogen component (A1) and the organicpolyisocyanate component (B). The item “Compound (S) content (%) inpolyurethane resin composition” refers to the compound (S) content (% byweight, excluding the comparative compound (S′)) in the polyurethaneresin composition based on the weight of the polyurethane resin when thecompound (S) is added. The measurements and evaluations were performedby the following methods.

[1] Method of Measuring Tensile Strength

The polyurethane resin solution or polyurethane resin composition wasapplied in a thickness of 0.7 mm on a glass plate that had beenrelease-treated, and dried at 70° C. for 3 hours in a circulating airdryer. The dried product was released from the glass plate to give afilm for tensile strength test having a thickness of approximately 0.2mm.

After the film for tensile strength test was allowed to stand in a roomhaving a temperature of 25° C. and a humidity of 65% RH for 1 day, thetensile strength was measured in accordance with JIS K 6251.

[2] Method of Measuring Permanent Set

A test piece produced in the same manner as in the production of thefilm for tensile strength test was allowed to stand in a room having atemperature of 25° C. and a humidity of 65% RH for 1 day. The test piecewas extended to 300% at a tensile speed of 50 cm/min. using aninstron-type tensile testing machine (autograph from ShimadzuCorporation) at a temperature of 25° C., and the extended state was keptfor 30 minutes. After returning to the initial state before extension atthe same speed as the tensile speed, a distance (L₅) between markedlines of 30 minutes later was measured. Based on the distance (L₅) and adistance (L₀) between the marked lines before testing, the permanent setwas determined from the following expression.Permanent set(%)=[1−(L ₅ −L ₀)/L ₀]×100

A smaller permanent set indicates better resistance to washing.

[3] Method of Measuring Moisture Permeability

The polyurethane resin solution or polyurethane resin composition wasapplied in a thickness of 25 μm on a glass plate that had beenrelease-treated, and dried at 70° C. for 3 hours in a circulating airdryer. The dried product was released from the glass plate to give afilm for moisture permeability test having a thickness of 7 μm.

The moisture permeability of the film for measuring moisturepermeability was measured in accordance with JIS L-1099-1998 CalciumChloride method (A-1).

[4] Method of Measuring Resistance to Water Pressure

Water resistance of a test piece produced in the same manner as in theproduction of the film for measuring moisture permeability was measuredin accordance with JIS L1092-1998 Hydrostatic pressure method (Method B:High pressure method). In the case where the test piece extends due tothe applied water pressure, the test piece was mounted on a tester aftera nylon taffeta (density: warp+woof=210 threads/2.54 cm equivalent) wasplaced on the test piece, and then measurement was performed.

[5] Method of Evaluating Resistance to Washing

The polyurethane resin solution or polyurethane resin composition wasapplied in a thickness of 10 μm on a release paper using a bar coater,and then dried at 120° C. for 2 minutes in an air oven to form a surfacelayer.

Next, 100 parts of SANPRENE LQ-120 (produced by Sanyo ChemicalIndustries, Ltd.), 9 parts of Colonate HL (produced by NipponPolyurethane Industry Co., Ltd.), and 0.02 parts of U-CAT SA102(produced by San-Apro Ltd.) were mixed to prepare an adhesive layerresin solution. The solution was applied on the surface layer to have athickness of 20 μm using a bar coater, and then dried at 120° C. for 2minutes in an air oven to form an adhesive layer on the surface layer.

A polyester taffeta (83 decitex) was further laminated over the adhesivelayer, and pressured-bonded at 1 MPa at 120° C. for 20 seconds using athereto-presser (Tabletop test press SA-302, produced by Tester SangyoCo., Ltd.) to prepare a moisture-permeable waterproof fabric.

The moisture-permeable waterproof fabric was washed in accordance withJIS L0217-103 method, and change in the external appearance wasevaluated. Fabrics with no changes in the external appearance wereevaluated as “Good”, and those with wrinkles or floatings were evaluatedas “Poor.”

TABLE 4-1 Example 1 Example 2 Example 3 Example 4 Example 5 Code ofpolyurethane resin or polyurethane resin composition U-1 U-2 U-3 U-4 U-5Tensile test Tensile strength (MPa) 88 86 80 80 85 Permanent set (%) 1314 12 17 14 Moisture permeability test Film thickness (μm) 7 7 7 7 7 andMoisture permeability (g/m² · 24 h) 11800 11500 10700 10200 12000 Waterpressure resistance Resistance to water pressure (mmH₂O) 30000 or more30000 or more 26000 24000 30000 or more test Resistance to washing testResistance to washing Good Good Good Good Good on fabric Oxyethylenegroup content (%) in polyurethane resin 60 60 60 60 60 Compound (S1)content (%) in polyurethane resin 0.05 0.05 0.05 4.7 0.05 Compound (S)content (%) in polyurethane resin composition 0 0 0 0 0 Example 6Example 7 Example 8 Example 9 Example 10 Code of polyurethane resin orpolyurethane resin composition U-6 U-7 U-8 U-9 U-10 Tensile test Tensilestrength (MPa) 84 76 83 78 81 Permanent set (%) 15 17 16 17 16 Moisturepermeability test Film thickness (μm) 7 7 7 7 7 and Moisturepermeability (g/m² · 24 h) 11600 10900 11000 11000 11000 Water pressureresistance Resistance to water pressure (mmH₂O) 30000 or more 2200030000 or more 23000 28000 test Resistance to washing test Resistance towashing Good Good Good Good Good on fabric Oxyethylene group content (%)in polyurethane resin 60 60 60 60 60 Compound (S1) content (%) inpolyurethane resin 0.015 0.05 0.05 0.05 0.47 Compound (S) content (%) inpolyurethane resin composition 0 0 0 0 0 Example 11 Example 12 Example13 Example 14 Example 15 Code of polyurethane resin or polyurethaneresin composition U-11 U-12 U-13 W-1 W-2 Tensile test Tensile strength(MPa) 83 74 90 77 75 Permanent set (%) 16 18 13 16 17 Moisturepermeability test Film thickness (μm) 7 7 7 7 7 and Moisturepermeability (g/m² · 24 h) 10500 11100 10100 12000 11200 Water pressureresistance Resistance to water pressure (mmH₂O) 30000 or more 2000030000 or more 23000 22000 test Resistance to washing test Resistance towashing Good Good Good Good Good on fabric Oxyethylene group content (%)in polyurethane resin 60 60 60 60 60 Compound (S1) content (%) inpolyurethane resin 0.05 0.05 4.8 0 0 Compound (S) content (%) inpolyurethane resin composition 0 0 0 0.05 0.05 Comparative ComparativeComparative Comparative Example 16 Example 1 Example 2 Example 3 Example4 Code of polyurethane resin or polyurethane resin composition W-3 U′-1U′-2 U′-3 W′-1 Tensile test Tensile strength (MPa) 80 68 64 69 62Permanent set (%) 15 21 20 20 22 Moisture permeability test Filmthickness (μm) 7 7 7 7 7 and Moisture permeability (g/m² · 24 h) 1020011300 11000 11100 11200 Water pressure resistance Resistance to waterpressure (mmH₂O) 30000 or more 12000 10000 11000 8000 test Resistance towashing test Resistance to washing Good Poor Poor Poor Poor on fabricOxyethylene group content (%) in polyurethane resin 60 60 60 60 60Compound (S1) content (%) in polyurethane resin 0 0 0 0 0 Compound (S)content (%) in polyurethane resin composition 4.0 0 0 0 0

INDUSTRIAL APPLICABILITY

The polyurethane resin (U) for moisture-permeable waterproof materialsand polyurethane resin composition (W) according to the presentinvention are excellent in all of the moisture permeability,waterproofness, and resistance to washing. Thus, they are especiallyuseful for production of moisture-permeable waterproof materials forwears for outdoor activities such as fishing and mountain climbing,skiing wears, wind breakers, athletic wears, golf wears, rain wears,casual coats, outdoor work wears, gloves, shoes, and mountaineeringequipment such as tents, or the like.

The invention claimed is:
 1. A polyurethane resin composition (W) formoisture-permeable waterproof materials, comprising a polyurethaneresin, and a compound (S), wherein the polyurethane resin is obtained byreacting an active hydrogen component (A2) that comprises an oxyethylenegroup-containing high molecular weight diol (a1) other than the compound(S) with an organic polyisocyanate component (B), the oxyethylenegroup-containing high molecular weight diol (a1) has a hydroxyl value of2 to 150 mg KOH/g, wherein the polyurethane resin and the compound (S)cannot react with each other, the compound (S) is represented by thefollowing formula (1):

wherein X¹ represents a residue produced by removing c piece(s) ofactive hydrogen atom(s) from an active hydrogen-containing compoundhaving a valence of m, the c representing an integer satisfying theinequality: 1≦c≦m, the m representing an integer of 1 to 20; X²represents a residue produced by removing one piece of active hydrogenatom from an active hydrogen-containing compound, and a plurality of X²smay be the same as or different from one another; X¹ and X² may be thesame as or different from each other; Y represents a residue produced byremoving all of carboxyl groups from an aromatic polycarboxylic acidhaving a valence of 3 or more, wherein an aromatic ring in Y consists ofcarbon atoms, the carbon atoms are each optionally bound to a halogenatom and/or a substituent other than a carboxyl group, and at least oneof the carbon atoms has no substituent; a represents an integer of notsmaller than 1; b represents an integer of not smaller than 0; and a andb satisfy the inequality: 2≦a+b≦d−2, wherein d represents the number ofhydrogen atoms bound to the carbon atoms forming the aromatic ring ofthe aromatic polycarboxylic acid when all of substituents including acarboxyl group in the aromatic polycarboxylic acid are substituted byhydrogen atoms.
 2. The polyurethane resin composition formoisture-permeable waterproof materials according to claim 1, whereinthe compound (S) has a hydroxyl value of 0, or 70 to 500 mg KOH/g. 3.The polyurethane resin composition for moisture-permeable waterproofmaterials according to claim 1, wherein the compound (S) includes theresidue Y at a concentration of 1.0 to 6.0 mmol/g.
 4. The polyurethaneresin composition for moisture-permeable waterproof materials accordingto claim 1, wherein the compound (S) has a carbonyl group concentrationof 3.0 to 20 mmol/g.
 5. The polyurethane resin composition formoisture-permeable waterproof materials according to claim 1, whereinthe aromatic polycarboxylic acid having a valence of 3 or more has astructure in which two carbon atoms adjacent to the carbon atom havingno substituent in the aromatic ring are each bound to a carboxyl group.6. The polyurethane resin composition for moisture-permeable waterproofmaterials according to claim 5, wherein a carboxyl group or groups arefurther bound to either one or both of carbon atoms that are adjacent tothe carbon atoms each bound to a carboxyl group.
 7. The polyurethaneresin composition for moisture-permeable waterproof materials accordingto claim 1, wherein the aromatic polycarboxylic acid having a valence of3 or more is at least one of trimellitic acid and pyromellitic acid. 8.The polyurethane resin composition for moisture-permeable waterproofmaterials according to claim 1, wherein the amount of the compound (S)based on the weight of the polyurethane resin is 0.01 to 10% by weight.9. The polyurethane resin composition for moisture-permeable waterproofmaterials according to claim 1, wherein the amount of the oxyethylenegroup in the polyurethane resin based on the weight of the polyurethaneresin is 20 to 80% by weight.
 10. The polyurethane resin composition formoisture-permeable waterproof materials according to claim 1, wherein,X¹ represents a residue produced by removing c piece(s) of activehydrogen atom(s) from an active hydrogen-containing compound having avalence of m selected from the group consisting of C₂-C₂₀ polyhydricalcohols, polyether polyols obtained by adding alkylene oxide to C₂-C₂₀polyhydric alcohols, C₂-C₂₀ aliphatic polyamines, and polyvalent thiolcompounds, m represents an integer of 2 to 20; and X² represents aresidue produced by removing one piece of active hydrogen atom from anactive hydrogen-containing compound selected from the group consistingof C₂-C₂₀ polyhydric alcohols, polyether polyols obtained by addingalkylene oxide to C₂-C₂₀ polyhydric alcohols, C₂-C₂₀ aliphaticpolyamines, and polyvalent thiol compounds.